Nonvolatile semiconductor memory element, nonvolatile semiconductor memory, and method for operating nonvolatile semiconductor memory element

ABSTRACT

According to an aspect of the present invention, there is provided a nonvolatile semiconductor memory element including: a semiconductor substrate including: a source region; a drain region; and a channel region; a lower insulating film that is formed on the channel region; a charge storage film that is formed on the lower insulating film and that stores data; an upper insulating film that is formed on the charge storage film; and a control gate that is formed on the upper insulating film, wherein the upper insulating film includes: a first insulting film; and a second insulating film that is laminated with the first insulating film, and wherein the first insulating film is formed to have a trap level density larger than that of the second insulating film.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.13/619,223, filed Sep. 14, 2012, which is a continuation of U.S.application Ser. No. 13/272,821, filed Oct. 13, 2011, which is acontinuation of U.S. application Ser. No. 12/405,626 filed on Mar. 17,2009, and is based upon and claims priority from Japanese PatentApplication No. 2008-206291 filed on Aug. 8, 2008, the entire contentsof each of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

An aspect of the present invention relates to a nonvolatilesemiconductor memory element, nonvolatile semiconductor memory, and amethod for operating the nonvolatile semiconductor memory element.

2. Description of the Related Art

A nonvolatile semiconductor memory element has a structure wherein atunnel insulating film, a charge storage layer, an upper insulatinglayer and a control gate are deposited on a semiconductor substrate. Thecharge storage layer may be formed of a conductive charge storage layeror may be formed of a non-conductive charge storage layer. In thedescription to follow, the nonvolatile semiconductor memory elementusing the conductive charge storage layer will be discussed as thefloating gate type and the nonvolatile semiconductor memory elementusing the non-conductive charge storage layer will be discussed as thefloating trap type.

With miniaturization (finer design rules) of the nonvolatilesemiconductor memory, it is necessary to make the upper insulating layerthinner. Problems introduced as the upper insulating layer becomesthinner will be discussed separately for the floating gate type and thefloating trap type.

In the floating gate type, with the upper insulating layer made thinner,the leak current from the conductive charge storage layer at the writingoperation is increased and it is made difficult to store a charge. Onthe other hand, in the floating trap type, with the upper insulatinglayer made thinner, at the erasing operation, electron injection fromthe control gate into the charge storage layer is increased and theerasing efficiency is degraded.

Thus, with the upper insulating layer made thinner, the leak currentcharacteristic is increased and the write operation in the floating gatetype and the erasing operation in the floating trap type are degraded.Thus, an upper insulating layer having a lower leak currentcharacteristic than that of former structure is required. The leakcurrent characteristic can be decreased by adopting a structure fortrapping an electron in the upper insulating layer.

To adopt the structure for trapping an electron in the upper insulatinglayer, while decreasing the leak current, there is a problem in that theelectron trapped at the write operation, the read operation, or theerasing operation is emitted during the data retaining time and causesthreshold fluctuation of the nonvolatile semiconductor memory element.JP-2007-193862-A discloses an art of suppressing emission of theelectron trapped in the upper insulating layer during the data retainingtime. In JP-2007-193862-A, a detrap pulse is applied after data iswritten into a nonvolatile semiconductor memory element. The detrappulse is applied, whereby the charge trapped in the upper insulatinglayer at the write operation can be pulled out, so that charge emissionfrom the upper insulating layer to the charge storage layer at the dataretaining time can be suppressed and threshold fluctuation of thenonvolatile semiconductor memory element can be suppressed. The detrappulse is applied, whereby charge emission from the upper insulatinglayer to the charge storage layer at the data retaining time can besuppressed and threshold fluctuation of the nonvolatile semiconductormemory element can be suppressed.

In the art, the inventor of the invention focused attention on the factthat while the charge can be pulled out from the upper insulating layerto the charge storage layer at the detrap pulse, a charge from thecontrol gate may be trapped in the upper insulating layer andconsequently the charge trapped in the upper insulating layer cannotsufficiently be pulled out. Consequently, the inventor found that thereis a possibility that threshold fluctuation of the nonvolatilesemiconductor memory element caused by charge emission from the upperinsulating layer to the charge storage layer at the data retaining timecannot sufficiently be suppressed.

SUMMARY OF THE INVENTION

According to an aspect of the present invention, there is provided anonvolatile semiconductor memory element including: a semiconductorsubstrate including: a source region that is formed in the semiconductorsubstrate; a drain region that is formed in the semiconductor substrate;and a channel region that is sandwiched between the source region andthe drain region; a lower insulating film that is formed on the channelregion; a charge storage film that is formed on the lower insulatingfilm and that stores data; an upper insulating film that is formed onthe charge storage film; and a control gate that is formed on the upperinsulating film, wherein the upper insulating film includes: a firstinsulting film; and a second insulating film that is laminated with thefirst insulating film, and wherein the first insulating film is formedto have a trap level density larger than that of the second insulatingfilm.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a sectional view to show the structure of a nonvolatilesemiconductor memory element according to a first embodiment of theinvention.

FIGS. 2A to 2C are step sectional views to show a manufacturing methodof the nonvolatile semiconductor memory element according to the firstembodiment.

FIG. 3 is a sectional view to show the structure of a nonvolatilesemiconductor memory element according to a second embodiment of theinvention.

FIGS. 4A to 4C are schematic drawings of a band diagram concerning anMIM capacitor in the second embodiment.

FIG. 5 is a sectional view to show the structure of a nonvolatilesemiconductor memory element according to a third embodiment of theinvention.

FIGS. 6A and 6B are step sectional views to show a manufacturing methodof the nonvolatile semiconductor memory element according to the thirdembodiment.

FIG. 7 is a sectional view to show the structure of a nonvolatilesemiconductor memory element according to a fourth embodiment of theinvention.

FIG. 8 is a block diagram to show NAND-type flash memory according to afifth embodiment of the invention.

FIG. 9 is a pattern plan view of a part of a memory cell array of thenonvolatile semiconductor memory according to the fifth embodiment.

FIG. 10 is an equivalent circuit diagram of the memory cell array of thenonvolatile semiconductor memory according to the fifth embodiment.

DETAILED DESCRIPTION OF THE INVENTION

Referring now to the accompanying drawings, there are shown embodimentsof the invention. In the accompanying drawings, identical or similarparts are denoted by the same or similar reference numeral. However, itis noted that the accompanying drawings are schematic and therelationship between each thickness and plan value, the thickness ratiobetween layers, and the like differ from those actually applied.Therefore, the specific thicknesses and values should be determinedconsidering the description that follows. The accompanying drawingscontain portions different in mutual value relationship, ratio, etc., ofcourse.

In the embodiments of the invention, “first conduction type” and “secondconduction type” are opposite conduction types to each other. If thefirst conduction type is n type, the second conduction type is p type;if the first conduction type is p type, the second conduction type is ntype. In the description to follow, the first conduction type is p typeand the second conduction type is n type; however, the first conductiontype may be n type and the second conduction type may be p type.

(First Embodiment)

FIG. 1 is a sectional view to show a nonvolatile semiconductor memoryelement according to a first embodiment of the invention. Thenonvolatile semiconductor memory element is an individual part of anonvolatile semiconductor memory and has an independent proper function.The nonvolatile semiconductor memory contains a plurality of nonvolatilesemiconductor memory elements.

The embodiment of the invention will be discussed with reference to FIG.1.

The nonvolatile semiconductor memory element according to the firstembodiment has a structure wherein a source region 2 and a drain region3 of second conduction type, such as n⁺ type, formed at a distance fromeach other are formed in a semiconductor substrate 1 of first conductiontype, such as p⁻ type. A region of the p⁻-type semiconductor substrate 1between the source region 2 and the drain region 3 becomes a channelregion. The superscript − of the p⁻ type represents that the p-typeimpurity concentration is low, and the superscript + of the n⁺ typerepresents that the n-type impurity concentration is high. The sourceregion 2 and the drain region 3 are formed by injecting phosphorus.

In the structure, a tunnel insulating film 4, a conductive chargestorage layer 5, an upper insulating layer 6 and a control gate 7 aredeposited on the channel region of the surface of the p⁻-typesemiconductor substrate 1. The tunnel insulating film 4, the conductivecharge storage layer 5 and the control gate 7 have thicknesses of 5 to10 nm, 5 to 100 nm and 5 to 100 nm respectively, for example. The upperinsulating layer 6 has a three-layer structure of a transmitting layer 6a, a trapping layer 6 b, and a blocking layer 6 c wherein thetransmitting layer 6 a, the trapping layer 6 b and the blocking layer 6c are deposited in order on the conductive charge storage layer 5. Thetransmitting layer 6 a, the trapping layer 6 b and the blocking layer 6c have thicknesses of 0.5 to 4 nm, 1 to 5 nm, and 4 to 20 nmrespectively, for example.

The tunnel insulating film 4 is functioning as a lower insulating film;the upper insulating layer 6 is functioning as an upper insulating film;the trapping layer 6 b is functioning as a first insulating film; theblocking layer 6 c is functioning as a second insulating film; and thetransmitting layer 6 a is functioning as a third insulating film.

Material of the upper insulating layer 6, namely, the transmitting layer6 a, the trapping layer 6 b and the blocking layer 6 c will be discussedbelow: As the trapping layer 6 b, a material having an electron traplevel density larger than that of a material of the blocking layer 6 cand the transmitting layer 6 a is used.

Preferably, the blocking layer 6 c uses a material to enable a film of asmall trap level density to be formed. For example, the blocking layer 6c is formed containing an SiO₂ film, an Al₂O₃ film, an LaAlSiO film, ora film formed by replacing at least a part of the oxygen atoms of theSiO₂ film, the Al₂O₃ film, or the LaAlSiO film with nitrogen atoms. Theblocking layer 6 c may be formed by laminating at least two of theaforementioned films. An SiO₂ film, an SiON film, an SiN film, an Al₂O₃film and an LaAlSiO film may be preferably used.

For example, the trapping layer 6 b is formed of a material includingthe same constituent elements as the material of the blocking layer 6 c,and the constituent-elements composition ratio of the trapping layer 6 bis a largely different from the stoichiometric ratio as compared withthat of the blocking layer 6 c, thereby enhancing the electron traplevel density of the trapping layer 6 b as compared with that of theblocking layer 6 c.

As another example of the trapping layer 6 b, a film with a specificelement added to the same material as the blocking layer 6 c or amaterial of the same constituent elements, whose composition ratio ischanged, as the blocking layer 6 c may be used. Such material is used,whereby the electron trap level density of the trapping layer 6 b can bemade larger than that of the blocking layer 6 c. As the elements to beadded, one or more elements of B, C, N, F, Al, Si, P, S, Cl, Ga, As, Ti,Y, Zr, La, Pr, Nd, Sm, Gd, Dy, Hf, or Ta are used. Particularly, it ispreferable to use a film acquired by adding Hf or Zr to the blockinglayer 6 c material. That is, if the blocking layer 6 c is SiO₂,preferably HfSiO or ZrSiO is used as the trapping layer 6 b. If theblocking layer 6 c is Al₂O₃, preferably HfAlO or ZrAlO is used as thetrapping layer 6 b.

As another example of the trapping layer 6 b, a film containing oxide,nitride, or oxynitride of Ti, Y, Zr, La, Pr, Nd, Sm, Gd, Dy, Hf, or Tais used. Such material is used, whereby the electron trap level densityof the trapping layer 6 b can be made larger than that of the blockinglayer 6 c. Particularly, preferably a film containing oxide, nitride, oroxynitride of any of Ti, Y, Zr, or Hf is used as the trapping layer 6 b.

As another example of the trapping layer 6 b, SiN is also used.

Materials of the trapping layer 6 b and the blocking layer 6 c forforming an electron trap on the interface between the trapping layer 6 band the blocking layer 6 c if the electron trap level density of thetrapping layer 6 b is insufficient can be used. The electron trapoccurring on the interface traps an electron instead of trapping anelectron by the trapping layer 6 b. For example, materials of entirelydifferent constituent elements between the blocking layer 6 c and thetrapping layer 6 b are used as the blocking layer 6 c and the trappinglayer 6 b, whereby an electron trap is formed on the interface betweenthe trapping layer 6 b and the blocking layer 6 c. For example, SiN canbe used as the trapping layer 6 b and Al₂O₃ can be used as the blockinglayer 6 c.

Preferably, as the transmitting layer 6 a, a film having a smallelectron trap level density is formed. For example, the transmittinglayer 6 a is formed of an SiO₂ film, an Al₂O₃ film, an LaAlSiO film, ora film formed by replacing at least a part of the oxygen atoms of theSiO₂ film, the Al₂O₃ film, or the LaAlSiO film with nitrogen atoms. Thetransmitting layer 6 a may be formed by laminating at least two of theaforementioned films. An SiO₂ film may be preferably used as thetransmitting layer 6 a. As the transmitting layer, a film made of thesame material as the blocking layer 6 c may be preferably used.

The preferred materials of the transmitting layer 6 a, the trappinglayer 6 b and the blocking layer 6 c have been described. The preferredmaterial combinations of the transmitting layer 6 a, the trapping layer6 b and the blocking layer 6 c are shown below in the form oftransmitting layer 6 a/trapping layer 6 b/blocking layer 6 c: Forexample, SiO₂/SiN/Al₂O₃, SiO₂/HfAlO/Al₂O₃, SiO₂/ZrAlO/Al₂O₃,SiO₂/TiAlO/Al₂O₃, SiO₂/HfSiO/Al₂O₃ and SiO₂/ZrSiO/Al₂O₃. As for thesecombinations, SiO₂ may be replaced with SiON, Al₂O₃ may be replaced withSiO₂, and SiO₂ may be replaced with Al₂O₃.

Preferably, the transmitting layer 6 a has a large leak currentcharacteristic relative to the blocking layer 6 c. To make the leakcurrent characteristic of the transmitting layer 6 a larger than that ofthe blocking layer 6 c, the film thickness of the transmitting layer 6 ais thinned as compared with the blocking layer 6 c. Particularly, tomake the leak current characteristic of the transmitting layer 6 a largerelative to the blocking layer 6 c, preferably the film thickness of thetransmitting layer 6 a is thinner than that of the blocking layer 6 c.The advantage provided by increasing the leak current characteristic ofthe transmitting layer 6 a to be larger than that of the blocking layer6 c will be discussed below: As an example wherein the leak currentcharacteristic of the transmitting layer 6 a is larger than that of theblocking layer 6 c, the case where the transmitting layer 6 a uses thesame material as the blocking layer 6 c and has a thin film thickness ascompared with the blocking layer 6 c will be discussed. At the writingoperation, the leak current characteristic of the transmitting layer 6 ais larger than that of the blocking layer 6 c and thus the electroninjection amount into the trapping layer 6 b exceeds the emission amountand an electron can be trapped effectively. On the other hand, at thedetrap pulse of applying a voltage of a different polarity from that atthe writing operation, the electron trapped in the trapping layer 6 b isemitted to the charge storage layer 5 effectively. That is, since theleak current characteristic of the transmitting layer 6 a is larger thanthat of the blocking layer 6 c, an electron is emitted effectively fromthe trapping layer 6 b to the charge storage layer 5; while, electroninjection from the control gate 7 to the trapping layer 6 b is blockedby the blocking layer 6 c. As described above, the upper insulatinglayer 6 adopts the three-layer structure of the transmitting layer 6 a,the trapping layer 6 b and the blocking layer 6 c, and the leak currentcharacteristic of the transmitting layer 6 a is made larger than that ofthe blocking layer 6 c, whereby effective detrapping is performed forthe charge storage layer 5 from the upper insulating layer 6.

For an NAND-type cell array application, as for the upper insulatinglayer 6, preferably the following expression is satisfied forsuppressing charge trapping in the trapping layer 6 b at the readingoperation and suppressing charge detrapping from the trapping layer 6 bat the standby time:0<(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)<(Φ−φ)/Vpass  (Expression 1)where EOT₁, EOT₂ and EOT₃ are equivalent oxide thicknesses of thetransmitting layer 6 a, the trapping layer 6 b and the blocking layer 6c respectively. Letting ∈_(Si) be dielectric constant of Si and filmthickness and dielectric constant of each film, be T_(n) and ∈_(n),equivalent oxide thickness EOT_(n) is given according to the followingexpression:EOT_(n) =T _(n)×∈_(Si)/∈_(n)  (Expression 2)

For a laminated film of two or more layers, the equivalent oxidethickness EOT_(n) is given according to the following expression:EOT_(n)=Σ_(i) T _(ni)×∈_(Si)/∈_(ni)  (Expression 3)

Φ is work function or electron affinity of the conductive charge storagelayer 5, φ is trap level of the trapping layer 6 b with the vacuum levelas the reference, and V_(pass) is the largest voltage given to anunselected cell on the same bit line as a read cell at the readingoperation of NAND-type flash memory.

Next, the reason why preferably the “Expression 1” described above issatisfied as for the upper insulating layer 6 to suppress chargetrapping in the trapping layer 6 b at the reading operation and suppresscharge detrapping from the trapping layer 6 b at the standby time is asfollows:

To suppress an electron trapping in the trapping layer 6 b at thereading operation, preferably the Fermi level of the conductive chargestorage layer 5 at the reading operation is positioned on the lowerenergy side than the trap level of the trapping layer 6 b. Therefore, tosuppress an electron trapping in the trapping layer 6 b at the readingoperation, letting the work function or electron affinity of theconductive charge storage layer 5 be Φ, the trap level of the trappinglayer 6 b with the vacuum level as the reference be φ, and the traplevel shift amount in the trapping layer 6 b caused by the readingoperation voltage applied thereto and the charge trapped in the chargestorage layer be V_(r), preferably the following expression issatisfied:Φ−(φ+V _(r))>0  (Expression 4)

Letting the voltage applied to the upper insulating layer 6 be V_(IPD),the trap level shift amount V_(r) in the trapping layer 6 b caused bythe reading operation voltage applied thereto takes the maximum valuegiven from the following “Expression 5” on the interface between thetrapping layer 6 b and the blocking layer 6 c:V _(r)=(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)×V _(IPD)  (Expression 5)“Expression 5” is assigned to “Expression 4” to obtainΦ−(φ+(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)×V _(IPD))>0  (Expression 6)

It is desirable to form the upper insulating layer 6 so that “Expression6” is satisfied even if V_(IPD) becomes the maximum value.

To form an NAND-type cell array, the maximum value of V_(IPD) is derivedas follows: At the NAND-type flash memory reading operation, it isnecessary to turn on all cells on the same bit line as the read cell.Thus, the largest voltage V_(pass) is applied to an unselected cell onthe same bit line as the read cell. Since V_(pass) is distributed to thetunnel insulating film 4 and the upper insulating layer 6, the maximumvalue of V_(IPD) does not exceed V_(pass). Therefore, the maximum valueof V_(IPD) is V_(pass).

In “Expression 6”, setting V_(IPD)=V_(pass),Φ−(φ+(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)×V _(pass))>0  (Expression 7)is obtained. V_(pass) is more than 0 V and is equal to or less than 10V.

“Expression 7” is modified to(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)<(Φ−φ)/V _(pass)  (Expression 8)

Since EOT_(n) (n=1 to 3)>0,0<(EOT₁+EOT₂)/(EOT₁+EOT₂+EOT₃)<(Φ−φ)/V _(pass)  (Expression 9)

Thus, it is understood that it is preferable to satisfy the relation in“Expression 1” to suppress charge trapping in the trapping layer 6 b atthe reading operation and suppress charge detrapping from the trappinglayer 6 b at the standby time.

Table 1 lists electron trap level energy Φ and dielectric constantsabout a plurality of materials used for the trapping layer 6 b.

TABLE 1 Trap depth Trap level Relative Composition (eV)*1 φ (eV)*2Permittivity Source Recital HfO2 0.3 2.8 25 IEDM, 2002, pp. 731-734 1.33.8 Appl. Phys. Lett. 80, No. 11, 18 Mar. 2002 0.5 3.0 0.7 3.2 0.8 3.3HfAlO 1.2 3.2 18 IEEE Electron Device Letters, Vol.29, No. 2, February2008 Hf/Al = 1 2.0 4.0 HfSiON 0.9 3.3 14 Jpn. J. Appl. Phys., Vol. 45,No. 4B (2006) Hf/Si = 1, N15% ZrO2 0.8 2.8 25 J. Appl. Phys., Vol. 87,No 12, 15 Jun. 2000 Si3N4 1.1 2.7 7 Solid State Electronics 44 (2000)949-958 1.5 3.1 Appl. Phys. Lett. Vol. 32, No. 5, 1 Mar. 1978 0.7 2.3 J.Appl. Phys., Vol. 44, No 10, October 1973 *1Energy level of electrontrap with energy of conduction band lower end of insulating film asreference *2Energy level of electron trap with vacuum level as reference

In Table 1, “Trap depth” denotes the energy level of electron trap withthe energy of the conduction band lower end of the insulating film asthe reference, and “Trap level” denotes the energy level of electrontrap with the vacuum level as the reference.

For the control gate 7 or the conductive charge storage layer 5, it isdesirable to use a material stable in a thermal step of impurityactivation. In addition to polysilicon, as material satisfying theabove-mentioned condition, nitride or carbide of Ti, Ta, or W and amaterial formed by adding Al or Si thereto is used. Table 2 listsrepresentative materials of the control gate 7 or the conductive chargestorage layer 5 and work functions.

TABLE 2 Work function Material φ (eV) Source Recital TiC 3.35 SmithellsMetal Reference Book. E. A. Brandes et al. edited 3.80 J. Less-CommonMetal 82. TiC(100) (1981) 69. TiN 2.91 Appl. Surf. Sci 146. (1999) 177.4.80 VLSI-sympo. 2002. 24. TiAlN 5.00-5.20 IEDM2001, 671. TiAlNy y~14.36-4.50 TiAlNy y < 1 TaC 3.14 Smithells Metal Reference Book. E. A.Brandes et al. edited 4.38 Surf. Sci. 239, (1990) L517. Ta/C = 1 4.73Ta/C = 2 TaN 4.00 Appl. Surf. Sci 146. (1999) 177. 5.00 Int. ElectronDevices Ta/N = 1 Meet. 01. 667 (2001). (IEDM2001, 667.) TaAlN 4.90IEEE-EDL 24. (2003) 298. TaSiN 4.40 J. Vac. Sci. Technol. B21(1) 11.N26% 4.27 VLSI-sympo. 2001. 47. WN 4.35 J. Vac. Sci. Technol. B21(1) 11.W/N = 1.5 “Work function” denotes the Fermi energy of metal with thevacuum level as the reference. The work functions of the materials canbe modulated to any desired values according to the composition, filmformation condition, thermal step after film formation, orientation ofcrystal, etc. To use a semiconductor of polysilicon, etc., doped withimpurities at a high concentration as the control gate or the conductivecharge storage layer, electron affinity corresponds to the workfunction; for example, it is known that the electron affinity of siliconcrystal is 4.05 eV. If polysilicon is used as the conductive chargestorage layer 5, “electron affinity” corresponds to the “work function”,and the “Expression 1” is adaptable.

Next, a manufacturing process of the nonvolatile semiconductor memoryelement according to the embodiment will be discussed with reference toFIGS. 2A to 2C. FIGS. 2A to 2C are step sectional views to show themanufacturing process of the nonvolatile semiconductor memory element.

First, as shown in FIG. 2A, an insulating film is formed on entire topsurface of a p⁻-type semiconductor substrate 1, such as a p⁻-type Sisubstrate. As the insulating film, a silicon oxide film is formed bythermal oxidation, for example. Next, the silicon oxide film is etched,thereby forming a first insulating film pattern exposing both end partsof the p⁻-type semiconductor substrate 1 where a source region 2 and adrain region 3 are to be formed. Next, for example, phosphorus ionimplementation is executed onto the surface of the p⁻-type semiconductorsubstrate 1 with the first insulating film pattern as a mask, therebyforming the n⁺-type source region 2 and drain region 3. Next, etching isperformed, thereby removing the first insulating film pattern.Consequently, the n⁺-type source region 2 and drain region 3 are formedin the surface of the p⁻-type semiconductor substrate 1.

Next, as shown in FIG. 2B, an insulating film which will become a tunnelinsulating film 4 is formed on entire top surface of the p⁻-typesemiconductor substrate 1. As the insulating film, a silicon oxide filmis formed by thermal oxidation, for example. The silicon oxide film isformed in a film thickness of 5 to 10 nm, for example. Next, forexample, polysilicon is deposited on the silicon oxide film by a CVDmethod to form a polysilicon film which will become a conductive chargestorage layer 5. The polysilicon film is formed in a film thickness of 5to 100 nm, for example. Next, for example, SiO₂ is deposited on thepolysilicon film by the CVD method to form an SiO₂ film which willbecome a transmitting layer 6 a. Next, for example, SiN is deposited onthe transmitting layer 6 a by the CVD method to form an SiN film whichwill become a trapping layer 6 b. Next, for example, SiO₂ is depositedon the trapping layer 6 b by the CVD method to form an SiO₂ film whichwill become a blocking layer 6 c.

The trap level density can be increased or decreased according to thefilm formation condition. By the impurities of C, Cl, etc. are containedwhen the trapping layer 6 b is formed by the CVD method, the trap levelis provided in the trapping layer 6 b. Therefore, for example, byforming the trapping layer 6 b while lowering the film formationtemperature, the trap level density can be increased. The transmittinglayer 6 a and the trapping layer 6 b are formed by the CVD method usingthe same material, and as the film formation condition, the temperatureat the film forming time of the trapping layer 6 b is set lower thanthat at the film forming time of the transmitting layer 6 a, therebyforming the transmitting layer 6 a and the trapping layer 6 b having atrap level density larger than that of the transmitting layer 6 a. Byforming the transmitting layer 6 a and the trapping layer 6 b in suchcondition, the trap level density of the trapping layer 6 b can be madelarger than that of the transmitting layer 6 a. Likewise, the blockinglayer 6 c and the trapping layer 6 b can be formed by the CVD methodusing the same material and adapting the film formation condition inwhich the temperature at the film forming time of the trapping layer 6 bis set to lower than that of the temperature at the film forming time ofthe blocking layer 6 c.

Next, for example, polysilicon is deposited on the blocking layer 6 c bythe CVD method to form a polysilicon film which will become a controlgate 7. The polysilicon film is formed in a film thickness of 5 to 100nm, for example.

Next, as shown in FIG. 2C, lithography is executed for the laminatedstructure made up of the silicon oxide film, the polysilicon film, theSiO₂ film, the SiN film, the SiO₂ film and the polysilicon film, therebypartially exposing the source region 2 and the drain region 3.Consequently, the laminated structure is formed wherein the tunnelinsulating film 4 formed of the silicon oxide film, the conductivecharge storage layer 5 formed of the polysilicon film, the transmittinglayer 6 a formed of the SiO₂ film, the trapping layer 6 b formed of theSiN film, the blocking layer 6 c formed of the SiO₂ film and the controlgate 7 formed of the polysilicon film are deposited in order. Thedescribed manufacturing process is executed, thereby forming thenonvolatile semiconductor memory element according to the firstembodiment shown in FIG. 1.

Next, a writing operation in the nonvolatile semiconductor memoryelement according to the first embodiment will be discussed. At thewriting operation, first, a positive voltage is applied to the controlgate 7 and an electron is injected into the conductive charge storagelayer 5 through the tunnel insulating film 4 from the semiconductorsubstrate 1. At this time, as the voltage applied to the control gate 7,the equivalent oxide field in the upper insulating layer 6 exceeds 0MV/cm and is equal to or less than 30 MV/cm and the time is in the rangeof 1 ns to 10 ms. More preferably, the equivalent oxide field is in therange of 10 MV/cm to 25 MV/cm and the time is in the range of 1 ns to0.1 ms. At this time, an electron is injected into the upper insulatinglayer 6 from the conductive charge storage layer 5 and is trapped. Theupper insulating layer 6 traps the electron, so that electron leak fromthe conductive charge storage layer 5 to the control gate 7 issuppressed. This voltage applied at the writing operation is referred toas a writing trap pulse. Next, a first detrap pulse different inpolarity from the above-mentioned voltage is applied. At this time, thefirst detrap pulse is characterized by the fact that at least either theabsolute voltage value or the time length of the first detrap pulse issmaller than the operating voltage at the writing operation. As thefirst detrap pulse, more preferably the equivalent oxide field in theupper insulating layer 6 exceeds 0 MV/cm and is equal to or less than 10MV/cm and the time is in the range of 1 ns to 0.1 ms. The first detrappulse is applied, whereby the electron trapped in the upper insulatinglayer 6 at the writing operation is emitted to the conductive chargestorage layer 5. As described above, in the embodiment, the upperinsulating layer 6 adopts the laminated structure of the transmittinglayer 6 a, the trapping layer 6 b and the blocking layer 6 c, the traplevel density of each of the transmitting layer 6 a and the blockinglayer 6 c is made smaller than that of the trapping layer 6 b, and theleak current characteristic of the transmitting layer 6 a is made higherthan that of the blocking layer 6 c, so that charge can be effectivelyemitted to the charge storage layer 5 by applying the first detrappulse.

When the first detrap pulse is applied, excessive holes may be trappedin the trapping layer 6 b. When excessive holes are trapped in thetrapping layer 6 b, if the excessively trapped holes are emitted at thestandby time, threshold fluctuation is caused to occur and reliabilityis degraded. Thus, a second detrap pulse of the same polarity as thewriting trap pulse is applied as required after the first detrap pulseis applied. The second detrap pulse is applied, whereby electrons isinjected into the upper insulating layer 6 to cancel out the excessiveholes. At this time, the electron amount injected into the upperinsulating layer 6 needs to be small as compared with the writing trappulse. Therefore, at least either the absolute voltage value or the timelength of the second detrap pulse needs to be smaller than the writingtrap pulse. As the second detrap pulse, more preferably the equivalentoxide field applied to the upper insulating layer 6 exceeds 0 MV/cm andis equal to or less than 10 MV/cm and the time is in the range of 1 nsto 0.1 ms.

In the nonvolatile semiconductor memory element according to theembodiment, charge emission from the upper insulating layer 6 at thedata retaining time is prevented, the threshold fluctuation during thedata retaining time is suppressed, and the reliability is enhanced.Particularly, in the embodiment, the upper insulating layer 6 adopts thelaminated structure of the transmitting layer 6 a, the trapping layer 6b and the blocking layer 6 c, the leak current characteristic of thetransmitting layer 6 a is made larger than that of the blocking layer 6c, and the trap level density of each of the transmitting layer 6 a andthe blocking layer 6 c is made smaller than that of the trapping layer 6b, so that charge can be effectively emitted to the charge storage layer5 by applying the first detrap pulse.

According to the embodiment, an electron is trapped in the trappinglayer 6 b at the writing operation, whereby the leak current from theconductive charge storage layer 5 to the control gate 7 at the writingoperation is suppressed and the threshold difference at the writingoperation is increased. Particularly, in the upper insulating layer 6according to the embodiment, the film thickness of the transmittinglayer 6 a is thinner than that of the blocking layer 6 c, and thus theleak current characteristic of the transmitting layer 6 a is larger thanthat of the blocking layer 6 c. Therefore, at the writing operation, thetransmitting layer 6 a allows an electric current to well flow ascompared with the blocking layer 6 c, so that more electrons are trappedin the trapping layer 6 b having a higher trap level density.

According to the embodiment, the electron trapped in the trapping layer6 b at the writing operation is detrapped to the conductive chargestorage layer 5 by applying a detrap pulse, whereby the stored chargeamount of the conductive charge storage layer 5 is increased, largethreshold difference relative to the applied voltage of the writing trappulse is obtained, and the operating voltage is decreased.

In the embodiment, after a first detrap pulse is applied, a seconddetrap pulse of a different polarity from the first detrap pulse isapplied, whereby the hole injected into the trapping layer 6 b at thefirst detrap pulse is canceled out. According to the operation, holeemission from the trapping layer 6 b at the data retaining time isprevented and the threshold fluctuation during the data retaining timeis suppressed.

(Second Embodiment)

FIG. 3 is a sectional view to show a nonvolatile semiconductor memoryelement according to a second embodiment of the invention.

The nonvolatile semiconductor memory element according to the secondembodiment differs in that an upper insulating layer 26 has a two-layerstructure of a trapping layer 26 b and a blocking layer 26 c from thenonvolatile semiconductor memory element according to the firstembodiment wherein the upper insulating layer 6 has the three-layerstructure of the transmitting layer 6 a, the trapping layer 6 b and theblocking layer 6 c.

That is, the nonvolatile semiconductor memory element according to thesecond embodiment has a structure wherein a source region 2 and a drainregion 3 of second conduction type, such as n⁺ type, formed at adistance from each other are formed in a semiconductor substrate 1 offirst conduction type, such as p⁻ type. In the structure, a tunnelinsulating film 4, a conductive charge storage layer 5, theabove-mentioned upper insulating layer 26 and a control gate 7 aredeposited on a channel region of the surface of the p⁻-typesemiconductor substrate 1. The tunnel insulating film 4, the conductivecharge storage layer 5 and the control gate 7 have thicknesses of 5 to10 nm, 5 to 100 nm and 5 to 100 nm respectively, for example. The upperinsulating layer 26 has the two-layer structure of the trapping layer 26b and the blocking layer 26 c wherein the trapping layer 26 b and theblocking layer 26 c are deposited in order on the conductive chargestorage layer 5. The trapping layer 26 b and the blocking layer 26 chave thicknesses of 1 to 5 nm and 4 to 20 nm respectively, for example.

Material of the upper insulating layer 26, namely, the trapping layer 26b and the blocking layer 26 c will be discussed below:

As the material of the trapping layer 26 b, material having a largeelectron trap level density as compared with that of the blocking layer26 c is used.

The same material as shown in the first embodiment can be used as thematerial of the trapping layer 26 b and the blocking layer 26 c. Thetrapping layer 26 b uses material having a large electron trap leveldensity as compared with the blocking layer 26 c.

The preferred material combinations of the trapping layer 26 b and theblocking layer 26 c are shown below as in the form of trapping layer 26b/blocking layer 26 c: For example, SiN/Al₂O₃, HfAlO/Al₂O₃, ZrAlO/Al₂O₃,TiAlO/Al₂O₃, HfSiO/Al₂O₃ and ZrSiO/Al₂O₃. As for these combinations,SiO₂ may be changed to SiON, Al₂O₃ may be changed to SiO₂, and SiO₂ maybe changed to Al₂O₃.

To form an NAND-type cell array, as for the upper insulating layer 26,preferably the following expression is satisfied for suppressing chargetrapping in the trapping layer 26 b at the reading operation andsuppressing charge detrapping from the trapping layer 26 b at thestandby time. The following expression is derived by assigning EOT₁=0 in“Expression 1” in the first embodiment:0<(EOT₂)/(EOT₂+EOT₃)<(Φ−φ)/V _(pass)  (Expression 10)

As material of the control gate 7 and the conductive charge storagelayer 5, similar material to that in the first embodiment is used.

A manufacturing process of the nonvolatile semiconductor memory elementaccording to the second embodiment differs from the first embodiment inthat the trapping layer 26 b is formed on a polysilicon film of theconductive charge storage layer 5 and the transmitting layer 6 a is notformed.

Next, a writing operation in the nonvolatile semiconductor memoryelement according to the second embodiment and a detrapping operationfor detrapping an electron from the upper insulating layer 26 will bediscussed. The writing operation is similar to those of the firstembodiment.

According to the nonvolatile semiconductor memory element according tothe embodiment, charge emission through the upper insulating layer 26 atthe data retaining time is suppressed, the threshold fluctuation duringthe data retaining time is suppressed, and the reliability is enhanced.Particularly, in the embodiment, the upper insulating layer 26 adoptsthe two-layer structure made up of the trapping layer 26 b on theconducive charge storage layer 5 side and the blocking layer 26 c havingthe small trap level density as compared with that of the trapping layer26 b on the control gate 7 side. Consequently, electrons is effectivelydetrapped from the upper insulating layer 26 by applying the firstdetrap pulse after the writing operation.

According to the embodiment, as in the first embodiment, an electron istrapped in the trapping layer 26 b at the writing operation, whereby theleak current from the conductive charge storage layer 5 to the controlgate 7 at the writing operation is suppressed and the thresholddifference at the writing operation is increased.

According to the second embodiment, as in the first embodiment, theelectron trapped in the trapping layer 6 b at the writing operation isdetrapped to the conductive charge storage layer 5 by applying a detrappulse, whereby the stored charge amount of the conductive charge storagelayer 5 is increased, large threshold difference relative to the appliedvoltage of the writing trap pulse is obtained, and the operating voltageis decreased.

According to the second embodiment, as in the first embodiment, after afirst detrap pulse is applied, a second detrap pulse of a differentpolarity from the first detrap pulse is applied, whereby the holeinjected into the trapping layer 26 b at the first detrap pulse iscanceled out. According to the operation, hole emission from thetrapping layer 26 b at the data retaining time is prevented and thethreshold fluctuation during the data retaining time is suppressed.

The reason why the electron is effectively detrapped by applying thefirst detrap pulse by adopting the two-layer structure of the upperinsulating layer 26 made up of the trapping layer 26 b on the conductivecharge storage layer 5 side and the blocking layer 26 c having the smalltrap level density as compared with that of the trapping layer 26 b onthe control gate 7 side is as follows:

FIGS. 4A to 4C are schematic drawings of a band diagram concerning anMIM capacitor provided by depositing an electrode A, an insulating film,and an electrode B. The insulating film of the MIM capacitor is made upof two layers of an insulating film A on the electrode A side and aninsulating film B on the electrode B side, and the trap level density ofthe insulating film A is larger than that of the insulating film B. Inthe nonvolatile semiconductor memory element according to the embodimentand the MIM capacitor in FIGS. 4A to 4C, the electrode A corresponds tothe conductive charge storage layer 5, the insulating film A correspondsto the trapping layer 26 b, the insulating film B corresponds to theblocking layer 26 c, and the electrode B corresponds to the control gate7. FIG. 4A shows a state in which a voltage is applied to neither theelectrode A nor the electrode B. In FIGS. 4A to 4C, the work functionsof the electrodes A and B are the same, but the types and the workfunctions of the electrodes need not be the same. Band gaps and filmthicknesses are also schematic and the relationship in FIGS. 4A to 4Cneed not be satisfied. Electron trap in the film modulates the potentialof the insulating film, but is not illustrated in FIGS. 4A to 4C.

As for the MIM capacitor, when a positive voltage is applied to theelectrode B, an electron is trapped in the insulating film A from theelectrode A as shown in FIG. 4B, because the electron trap level densityof the insulating film A is large. At this time, the electron amounttrapped in the insulating film B is small as compared with the electronamount trapped in the insulating film A as it is negligible. Next, whena negative voltage is applied to the electrode B, the electron trappedin the insulating film A is detrapped to the electrode A as shown inFIG. 4C. Since the insulating film B exists, electron injection into theinsulating film A from the electrode B is suppressed. Since the electrontrap level density of the insulating film B is small, electron trap ofthe insulating film B is small. Consequently, when a negative bias isapplied to the electrode B, the electron trapped in the insulating filmA is detrapped efficiently. By forming the insulating films different intrap level density, the electron trapped in the insulating film A iseffectively detrapped by applying a detrap pulse.

From the description given above, it is seen that the electron trappedin the upper insulating layer 26 at the writing operation is effectivelydetrapped by applying the first detrap pulse by adopting the two-layerstructure made up of the trapping layer 26 b on the conductive chargestorage layer 5 side and the blocking layer 26 c having the smallelectron trap level density as compared with that of the trapping layer26 b on the control gate 7 side, as the upper insulating layer 26.

(Third Embodiment)

FIG. 5 is a sectional view to show a nonvolatile semiconductor memoryelement according to a third embodiment of the invention.

The third embodiment of the invention will be discussed below withreference to the accompanying drawings:

The nonvolatile semiconductor memory element according to the thirdembodiment has a structure wherein a source region 2 and a drain region3 of second conduction type, such as n⁺ type, formed at a distance fromeach other are formed in a semiconductor substrate 1 of first conductiontype, such as p⁻ type. A region of the p⁻-type semiconductor substrate 1between the source region 2 and the drain region 3 becomes a channelregion.

In the structure, a tunnel insulating film 4, a non-conductive chargestorage layer 35, an upper insulating layer 36 and a control gate 7 aredeposited on the p⁻-type semiconductor substrate 1. The tunnelinsulating film 4, the non-conductive charge storage layer 35 and thecontrol gate 7 have thicknesses of 2 to 10 nm, 2 to 20 nm and 5 to 100nm respectively, for example. The upper insulating layer 36 has athree-layer structure of a blocking layer 36 c, a trapping layer 36 b,and a transmitting layer 36 a, wherein the blocking layer 36 c, thetrapping layer 36 b and the transmitting layer 36 a are deposited inorder on the non-conductive charge storage layer 35. The blocking layer36 c, the trapping layer 36 b and the transmitting layer 36 a havethicknesses of 4 to 20 nm, 1 to 5 nm and 0.5 to 4 nm respectively, forexample.

Material of the upper insulating layer 36, namely, the blocking layer 36c, the trapping layer 36 b and the transmitting layer 36 a will bediscussed below:

As the material of the blocking layer 36 c, the trapping layer 36 b andthe transmitting layer 36 a, the same material as the material shown inthe first embodiment can be used.

Next, preferred material combinations of the blocking layer 36 c, thetrapping layer 36 b and the transmitting layer 36 a will be discussed.

The preferred material combinations of the blocking layer 36 c, thetrapping layer 36 b and the transmitting layer 36 a are shown below inthe form of blocking layer 36 c/trapping layer 36 b/transmitting layer36 a: For example, Al₂O₃/SiN/SiO₂, Al₂O₃/HfAlO/SiO₂, Al₂O₃/ZrAlO/SiO₂,Al₂O₃/TiAlO/SiO₂, Al₂O₃/HfSiO/SiO₂ and Al₂O₃/ZrSiO/SiO₂. As for thesecombinations, SiO₂ may be changed to SiON, Al₂O₃ may be changed to SiO₂,and SiO₂ may be changed to Al₂O₃.

Preferably, the transmitting layer 36 a has a large leak currentcharacteristic relative to the blocking layer 36 c. To make the leakcurrent characteristic of the transmitting layer 36 a larger than thatof the blocking layer 36 c, the film thickness of the transmitting layer36 a is thinned, a material having a small dielectric constant is used,or a material having a small film thickness and a small dielectricconstant is used as compared with the blocking layer 36 c. Particularly,to make the leak current characteristic of the transmitting layer 36 alarger than that of the blocking layer 36 c, preferably the filmthickness of the transmitting layer 36 a is formed smaller than that ofthe blocking layer 36 c.

As for the upper insulating layer 36, preferably the followingexpression is satisfied for suppressing charge trapping in the trappinglayer 36 b during standby time and effectively trapping an electron atthe erasing operation:0<Φ−φ≦(EOT₁+EOT₂)/(EOT_(total))×V _(erase)  (Expression 11)where EOT₁ and EOT₂ are equivalent oxide thicknesses of the transmittinglayer 36 a and the trapping layer 36 b respectively. EOT_(total) is thesum total of the equivalent oxide thicknesses of the tunnel insulatingfilm 4, the non-conductive charge storage layer 35 and the upperinsulating layer 36. V_(erase) is the electric potential differencebetween the semiconductor substrate 1 and the control gate 7 at theerasing operation. Φ is work function of the control gate 7 and φ istrap level of the trapping layer 36 b with the vacuum level as thereference.

Next, the reason why preferably the “Expression 11” described above issatisfied as for the upper insulating layer 36 to suppress chargetrapping in the trapping layer 36 b during standby time and enhanceelectron trapping at the erasing trap pulse is as follows:

To suppress charge trapping in the trapping layer 36 b during standbytime, preferably the Fermi level of the control gate 7 is positioned onthe lower energy side than the trap level of the trapping layer 36 bduring standby time. Therefore, to suppress charge trapping in thetrapping layer 36 b during standby time, letting the work function ofthe control gate 7 be Φ and the trap level of the trapping layer 36 bwith the vacuum level as the reference be φ, preferably the followingexpression is satisfied:0<Φ−φ  (Expression 12)On the other hand, since an electron needs to be trapped at the traplevel of the trapping layer 36 b at the erasing operation, preferablythe work function of the control gate 7 exceeds the trap level of thetrapping layer 36 b at the erasing operation. Therefore, letting themaximum value of voltage drop of the trap level of the trapping layer 36b in an erase bias be Vf, preferably the following expression issatisfied:Φ+(φ+Vf)≦0  (Expression 13)

Letting the electric potential difference between the channel region andthe control gate 7 at the erasing operation be V_(erase), the maximumvalue of voltage drop of the trap level of the trapping layer 36 baccording to the erase bias, Vf, is given according to the followingexpression:Vf=(EOT₁+EOT₂)/(EOT_(total))×V _(erase)  (Expression 14)

From “Expression 12”, “Expression 13”, and “Expression 14”,0<Φ−φ≦(EOT₁+EOT₂)/(EOT_(total))×V _(erase)  (Expression 15)

Thus, it is preferable to satisfy the “Expression 11” as for the upperinsulating layer 36 to suppress charge trapping in the trapping layer 36b during standby time and enhance electron trapping at the erasing trappulse.

If the control gate 7 is made of polysilicon, “electron affinity”corresponds to the “work function” and a similar expression can be used.

Next, a manufacturing process of the nonvolatile semiconductor memoryelement according to the embodiment will be discussed with reference toFIGS. 6A and 6B. FIGS. 6A and 6B are step sectional views to show themanufacturing process of the nonvolatile semiconductor memory element.

First, as shown in FIG. 6A, as in the first embodiment, an n⁺-typesource region 2 and drain region 3 are formed in the surface of ap⁻-type semiconductor substrate 1. Next, an insulating film which willbecome a tunnel insulating film 4 is formed on entire top surface of thep⁻-type semiconductor substrate 1. As the insulating film, a siliconoxide film is formed by thermal oxidation, for example. The siliconoxide film is formed in a film thickness of 2 to 10 nm, for example.Next, for example, silicon nitride is deposited on the silicon oxidefilm by a CVD method to form a silicon nitride film which will become anon-conductive charge storage layer 35. The silicon nitride film isformed in a thickness of 2 to 20 nm, for example. Next, for example,SiO₂ is deposited on the silicon nitride film by the CVD method to forman SiO₂ film which will become a blocking layer 36 c. Next, for example,SiN is deposited on the blocking layer 36 c by the CVD method to form anSiN film which will become a trapping layer 36 b. Next, for example,SiO₂ is deposited on the trapping layer 36 b by the CVD method to forman SiO₂ film which will become a transmitting layer 36 a. For the films,the trap level density is increased or decreased according to the filmformation condition as in the first embodiment. When the trapping layer36 b is formed, the trap level density can also be increased by loweringthe film formation temperature as in the first embodiment. Next, forexample, polysilicon is deposited by the CVD method to form apolysilicon film. The polysilicon film is formed in a film thickness of5 to 100 nm, for example.

Next, as shown in FIG. 6B, lithography is executed for the laminatedstructure made up of the silicon oxide film, the silicon nitride film,the SiO₂ film, the SiN film and the polysilicon film, thereby partiallyexposing the source region 2 and the drain region 3. Consequently, thelaminated structure is formed wherein the tunnel insulating film 4formed of the silicon oxide film, the non-conductive charge storagelayer 35 formed of the silicon nitride film, the blocking layer 36 cformed of the SiO₂ film, the trapping layer 36 b formed of the SiN film,the transmitting layer 6 a formed of the SiO₂ film and the control gate7 formed of the polysilicon film are deposited in order. The describedmanufacturing process is executed, thereby forming the nonvolatilesemiconductor memory element according to the third embodiment shown inFIG. 5.

Next, an erasing operation in the nonvolatile semiconductor memoryelement according to the third embodiment will be discussed. At theerasing operation, a voltage is applied so that the control gate 7becomes a negative voltage relative to the semiconductor substrate 1 anda hole is injected into the non-conductive charge storage layer 35 fromthe semiconductor substrate 1. The absolute value of the voltage appliedbetween the control gate 7 and the semiconductor substrate 1 at theerasing operation exceeds 0 MV/cm as the equivalent oxide field and isequal to or less than 25 MV/cm and the time is in the range of 1 ns to10 ms. More preferably, the equivalent oxide field is in the range of 10MV/cm to 25 MV/cm and the time is in the range of 1 ns to 0.1 ms.

At this time, an electron is injected into the trapping layer 36 b fromthe control gate 7 and is trapped. The upper insulating layer 36 trapsthe electron, so that the leak current passing through the upperinsulating layer 36 from the control gate 7 is suppressed. In the thirdembodiment, since the electron is trapped in the upper insulating layer36 at the erasing operation, an erasing trap pulse is applied to injectthe electron. Next, a first detrap pulse different in polarity from theabove-mentioned voltage is applied. In the first detrap pulse, at leasteither the absolute voltage value or the first detrap pulse applyingtime is smaller than the operating voltage at the erasing trap pulse. Asthe first detrap pulse, more preferably the equivalent oxide fieldexceeds 0 MV/cm and is equal to or less than 10 MV/cm and the time is inthe range of 1 ns to 0.1 ms. The first detrap pulse is applied, wherebythe electron trapped in the upper insulating layer 36 at the erasingtrap pulse is emitted to the control gate 7. In the embodiment, theupper insulating layer 36 adopts the laminated structure of the blockinglayer 36 c, the trapping layer 36 b and the transmitting layer 36 a, andthe leak current characteristic of the transmitting layer 36 a is madehigher than that of the blocking layer 36 c, so that an electron iseffectively emitted from the upper insulating layer 36 to the controlgate 7 by applying the first detrap pulse. The principle of enabling anelectron to be effectively emitted from the upper insulating layer 36 tothe control gate 7 is similar to that described in the first embodiment.That is, since the transmitting layer 36 a has the high leak currentcharacteristic, when the first detrap pulse is applied, an electron iseffectively emitted from the trapping layer 36 b through thetransmitting layer 36 a to the control gate 7, and on the other hand,electron injection into the trapping layer 36 b through the blockinglayer 36 c from the non-conductive charge storage layer 35 is suppressedbecause the leak current characteristic of the blocking layer 36 c islow.

When the first detrap pulse is applied, excessive holes may be trappedin the trapping layer 36 b. If the excessively trapped holes are emittedat the standby time, threshold fluctuation is caused to occur andreliability is degraded. Thus, a second detrap pulse of the samepolarity as the erasing trap pulse is applied as required after thefirst detrap pulse is applied. The second detrap pulse is applied,whereby electrons is injected into the upper insulating layer 36 tocancel out the excessive holes in the upper insulating layer 36. Theelectron amount injected into the upper insulating layer 36 in thesecond detrap pulse application time needs to be smaller than that inthe erasing trap pulse application time. Therefore, at least either theabsolute voltage value or the time length of the second detrap pulseneeds to be smaller than the erasing trap pulse. As the second detrappulse, more preferably, the equivalent oxide field exceeds 0 MV/cm andis equal to or less than 10 MV/cm, and the time is in the range of 1 nsto 0.1 ms.

In the embodiment, by performing the described operation, chargeemission at the data retaining time from the upper insulating layer 36is prevented, the threshold fluctuation during the data retaining timeis suppressed, and the reliability is enhanced. Particularly, asdescribed above, in the embodiment, the upper insulating layer 36 adoptsthe laminated structure (three-layer structure) of the blocking layer 36c, the trapping layer 36 b and the transmitting layer 36 a, and the leakcurrent characteristic of the transmitting layer 36 a is made higherthan that of the blocking layer 36 c, so that an electron is effectivelyemitted from the upper insulating layer 36 to the control gate 7 byapplying the first detrap pulse.

As the described operation is performed, according to the nonvolatilesemiconductor memory element according to the third embodiment, anelectron is trapped in the trapping layer 36 b at the erasing operation,whereby the electric field applied on the upper insulating layer 36 isweakened and the electric field applied on the tunnel insulating film 4and the non-conductive charge storage layer 35 is strengthened.Consequently, electron emission from the non-conductive charge storagelayer 35 to the semiconductor substrate 1 and hole injection into thenon-conductive charge storage layer 35 from the semiconductor substrate1 are performed efficiently. An electron is trapped in the trappinglayer 36 b, whereby the electron barrier of the insulating film from thecontrol gate 7 to the trapping layer 36 b is increased. Accordingly, itis made possible to improve the erasing operation speed and decrease theoperating voltage. Particularly, in the upper insulating layer 36according to the embodiment, the film thickness of the transmittinglayer 36 a is thinner than that of the blocking layer 36 c, and thus theleak current characteristic of the transmitting layer 36 a is largerthan that of the blocking layer 36 c. Therefore, when the erasing trappulse is applied, the transmitting layer 36 a allows an electric currentto well flow as compared with the blocking layer 36 c, so that moreelectrons are trapped in the trapping layer 36 b having a higher traplevel density, so that the electrons are trapped in the trapping layer36 b effectively.

The blocking layer 36 c also suppresses charge move between thenon-conductive charge storage layer 35 and the trapping layer 36 bduring the write operation, the erasing operation, and the dataretaining time.

In the third embodiment, after a first detrap pulse is applied, a seconddetrap pulse of a different polarity from the first detrap pulse isapplied, whereby the hole injected into the trapping layer 36 b at thefirst detrap pulse is canceled out. According to the operation, holeemission from the trapping layer 36 b at the data retaining time isprevented, and the threshold fluctuation during the data retaining timeis suppressed.

(Fourth Embodiment)

FIG. 7 is a sectional view to show a nonvolatile semiconductor memoryelement according to a fourth embodiment of the invention.

The nonvolatile semiconductor memory element according to the fourthembodiment differs in that an upper insulating layer 46 has a two-layerstructure of a blocking layer 46 c and a trapping layer 46 b from thenonvolatile semiconductor memory element according to the thirdembodiment wherein the upper insulating layer 36 has the three-layerstructure of the blocking layer 36 c, the trapping layer 36 b and thetransmitting layer 36 a.

That is, the nonvolatile semiconductor memory element according to thefourth embodiment has a structure wherein a source region 2 and a drainregion 3 of second conduction type, such as n⁺ type, formed at adistance from each other are formed in a semiconductor substrate 1 offirst conduction type, such as p⁻ type. In the structure, a tunnelinsulating film 4, a non-conductive charge storage layer 35, theabove-mentioned upper insulating layer 46 and a control gate 7 aredeposited on a channel region of the surface of the p⁻-typesemiconductor substrate 1. The tunnel insulating film 4, thenon-conductive charge storage layer 35 and the control gate 7 havethicknesses of 2 to 10 nm, 2 to 20 nm and 5 to 100 nm respectively, forexample. The upper insulating layer 46 has the two-layer structurewherein the blocking layer 46 c and the trapping layer 46 b aredeposited in order on the non-conductive charge storage layer 35. Theblocking layer 46 c and the trapping layer 46 b have thicknesses of 4 to20 nm and 1 to 5 nm respectively, for example.

Material of the upper insulating layer 46, namely, the blocking layer 46c and the trapping layer 46 b will be discussed below: As the materialof the blocking layer 46 c, material having a small trap level densityas compared with that of the trapping layer 46 b is used. The samematerial as shown in the first embodiment can be used as the material ofthe blocking layer 46 c and the trapping layer 46 b.

The preferred material combinations of the blocking layer 46 c and thetrapping layer 46 b are shown below as in the form of blocking layer 46c/trapping layer 46 b: For example, Al₂O₃/SiN, Al₂O₃/HfAlO, Al₂O₃/ZrAlO,Al₂O₃/TiAlO, Al₂O₃/HfSiO and Al₂O₃/ZrSiO. As for these combinations,SiO₂ may be changed to SiON or SiN, Al₂O₃ may be changed to SiO₂, andSiO₂ may be changed to Al₂O₃.

As for the upper insulating layer 46, preferably the followingexpression is satisfied for suppressing charge trapping in the trappinglayer 46 b during standby time and charge trapping effectively at theerasing operation. The following expression can be derived by assigningEOT₁=0 in the third embodiment:0<Φ−φ≦(EOT₂)/(EOT_(total))×V _(erase)  (Expression 16)

A manufacturing process of the nonvolatile semiconductor memory elementaccording to the embodiment differs from the third embodiment in thatthe control gate 7 is formed on the trapping layer 46 b and thetransmitting layer is not formed on the trapping layer 46 b.

Next, an erasing operation in the nonvolatile semiconductor memoryelement according to the fourth embodiment and a detrapping operationfor detrapping an electron from the upper insulating layer 46 will bediscussed. The erasing operation is similar to those of the thirdembodiment. In the fourth embodiment, the upper insulating layer 46adopts the two-layer structure made up of the blocking layer 46 c on thenon-conductive charge storage layer 35 side and the trapping layer 46 bhaving the large charge trap level density as compared with that of theblocking layer 46 c on the control gate 7 side. In the fourthembodiment, charge is effectively emitted from the upper insulatinglayer 46 by applying the first detrap pulse. The principle of enablingcharge to be effectively emitted from the upper insulating layer 46 issimilar to that described in the second embodiment. That is, thestructure according to the embodiment is adopted, whereby when theerasing trap pulse is applied, an electron is easily injected into theupper insulating layer 46 from the control gate 7, and on the otherhand, when the detrap pulse is applied, charge move from thenon-conductive charge storage layer 35 to the upper insulating layer 46is suppressed. Consequently, the electron trapped in the upperinsulating layer 46 at the erasing operation is effectively detrapped byapplying the first detrap pulse.

As described above, according to the fourth embodiment, the two-layerstructure of the upper insulating layer 46 made up of the blocking layer46 c on the non-conductive charge storage layer 35 side and the trappinglayer 46 b having the large electron trap level density as compared withthat of the blocking layer 46 c on the control gate 7 side is adopted,whereby the electron trapped in the upper insulating layer 46 at theerasing operation is effectively detrapped by applying the first detrappulse. Therefore, charge emission through the upper insulating layer 46at the data retaining time is prevented, and the threshold fluctuationduring the data retaining time is suppressed.

In the embodiment, after a first detrap pulse is applied, a seconddetrap pulse of a different polarity from the first detrap pulse isapplied, whereby the hole injected into the trapping layer 46 b at thefirst detrap pulse is detrapped in the control gate 7, hole emissionthrough the upper insulating layer 46 at the data retaining time isprevented, the threshold fluctuation during the data retaining time issuppressed, and the reliability is enhanced.

According to the fourth embodiment, an electron is trapped in thetrapping layer 46 b at the erasing trap pulse, whereby the electricfield applied on the upper insulating layer 46 is weakened and theelectric field applied on the tunnel insulating film 4 and thenon-conductive charge storage layer 35 is strengthened. Consequently,electron emission from the non-conductive charge storage layer 35 to thesemiconductor substrate 1 and hole injection into the non-conductivecharge storage layer 35 from the semiconductor substrate 1 are performedefficiently, and it is made possible to improve the erasing operationspeed and decrease the operating voltage.

(Fifth Embodiment)

FIG. 8 is a block diagram to show NAND-type flash memory as nonvolatilesemiconductor memory according to a fifth embodiment of the invention.As shown in FIG. 8, the nonvolatile semiconductor memory according tothe embodiment includes a memory cell array 51 formed by arranging thenonvolatile semiconductor memory elements, for example, according to thefirst embodiment and a detrap pulse supply circuit 59 for supplying adetrap pulse to the control gate 7 of a memory cell for pulling outcharge from the upper insulating layer 6 after data is written into thenonvolatile semiconductor memory element.

As shown in FIG. 8, the NAND-type flash memory according to the fifthembodiment is made up of the memory cell array 51, a row decoder 52, acolumn decoder 53, a column selector 54, a sense amplifier and latchcircuit 55, a read output circuit 56, a write input circuit 57, awriting/erasing control circuit 58 for supplying a requiredwriting/erasing voltage or pulse signal in accordance with the operationmode and the detrap pulse supply circuit 59. The detrap pulse supplycircuit 59 may be formed in the writing/erasing control circuit 58.

After data is written by injecting charge of a first polarity into theconductive charge storage layer 5 from the semiconductor substrate 1 byapplying a voltage to a memory cell, the detrap pulse supply circuit 59supplies a detrap pulse of applying a voltage of a different polarityfrom the voltage applied at the writing operation between the controlgate 7 and the semiconductor substrate 1 of the nonvolatilesemiconductor memory element for emitting the charge of the firstpolarity trapped in the upper insulating layer 6 at the writing trappulse from the upper insulating layer 6. After applying the detrappulse, the detrap pulse supply circuit 59 may further apply a seconddetrap pulse. The second detrap pulse is a voltage of the same polarityas the voltage at the writing operation. The second detrap pulse isapplied, whereby the charge of the first polarity is injected into theupper insulating layer 6 into which the charge of the second polarity isinjected at the first detrap pulse, thereby canceling out the excessivecharge of the second polarity.

Next, the memory cell array 51 in FIG. 8 will be discussed. FIG. 9 is apattern plan view of a part of the memory cell array 51. In theembodiment, memory implementing the memory cell array 51 is formed ofthe nonvolatile semiconductor memory elements according to the firstembodiment. In FIG. 9, bit lines are not shown. FIG. 10 is an equivalentcircuit diagram of the memory cell array 51 shown in FIG. 9. In thememory cell array 51 shown in FIGS. 9 and 10, each NAND cell unit 60includes cell transistors M1 to M8 connected in series and selecttransistors S1 and S2 placed at both ends of the cell transistors.Select gate lines SG1 and SG2 are connected to gates of the selecttransistors S1 and S2, and control gate 7 lines (word lines) CG1 to CG8are connected to the control gates 7 of the memory cells M1 to M8. Bitlines BL1, BL2, . . . are connected to a drain of the select transistorS1 of each NAND cell unit 60, and a source line SL is connected to asource of the select transistor S2. Although eight cell transistors areconnected in series in the embodiment, the number of the celltransistors is not limited to eight; for example, it may be 16 or 32.

A writing operation and a detrapping operation according to thenonvolatile semiconductor memory according to the embodiment are similarto those of the first embodiment.

According to the nonvolatile semiconductor memory according to theembodiment, advantages similar to those of the first embodiment can beaccomplished.

In the fifth embodiment, the memory cell array provided by arranging thenonvolatile semiconductor memory elements according to the firstembodiment has been described, but the memory cell array may be providedby arranging the nonvolatile semiconductor memory elements according toany of the second to fourth embodiments. A detrap pulse supply circuitfor a memory cell array provided by arranging the nonvolatilesemiconductor memory elements according to the third or fourthembodiment is used will be discussed. After data is erased by emittingcharge having a first polarity from the non-conductive charge storagelayer 5 to the semiconductor substrate 1 by applying a voltage, thedetrap pulse supply circuit supplies a detrap pulse having a polaritydifferent from the erasing trap pulse to the control gate 7 for emittingthe first polarity charge trapped in the upper insulating layer 36 atthe erasing trap pulse therefrom. After applying the detrap pulse, thedetrap pulse supply circuit may further apply a second detrap pulse. Thesecond detrap pulse has the same polarity as the erasing operationvoltage. The second detrap pulse is applied, whereby the excessivecharge of the second polarity which is trapped at the first detrappulse, is detrapped from the upper insulating layer 36.

It is to be understood that the invention is not limited to the first tofifth embodiments described above and that the invention can be embodiedin various modifications without departing from the spirit and scope ofthe invention. The embodiments described above may be combined asrequired. For example, some components may be deleted from allcomponents disclosed in the embodiments described above.

In the first to fifth embodiments, the upper insulating layer adoptingthe two-layer or three-layer structure have been described. However, theupper insulating layer is not limited to the two-layer or three-layerstructure. For example, the upper insulating layer may adopt afour-or-more-layer structure.

The upper insulating layer may be formed of one layer. When the upperinsulating layer is formed of one layer, for example, it may adopt astructure wherein the electron trap level density is changedcontinuously along the film thickness direction. For example, tocontinuously lessen the electron trap level density along the filmthickness direction from the conductive charge storage layer 5 to thecontrol gate 7, the upper insulating layer can be formed by lesseningthe difference of the constituent-element composition ratio of the upperinsulating layer from the stoichiometric ratio from the conductivecharge storage layer 5 to the control gate 7. Such a structure isadopted, whereby the amount of electron injected into the upperinsulating layer from the control gate 7 is small as compared with theamount of electron emitted from the upper insulating layer to theconductive charge storage layer 5 at the first detrap pulse.Consequently, the electron trapped in the upper insulating layer at thewriting operation can be effectively detrapped by applying the firstdetrap pulse. Therefore, at the data retaining time, charge emissionthrough the upper insulating layer and the threshold fluctuation can besuppressed.

In the first to fifth embodiments, the electrically writable anderasable nonvolatile semiconductor memory element, particularly, theNAND-type flash memory has been shown. However, the invention can alsobe applied to NOR-type, AND-type, and DINOR type nonvolatilesemiconductor memory elements, NANO-type flash memory into which themerits of the NOR type and the NAND type are merged, a 3Tr-NAND-typenonvolatile semiconductor memory element having a structure wherein onememory element is sandwiched between two select transistors, and thelike.

In the first to fifth embodiments, the specific shapes, the specificsizes, and the specific materials have been shown, but the shapes, thesizes and the materials in the embodiments are shown by way of example;any other shape, size and material may be adopted without departing fromthe spirit and scope of the invention as long as the advantages of theinvention can be demonstrated.

For example, in the first to fifth embodiments, the laminated structureis provided on the Si substrate. However, the laminated structure neednot be formed on the Si substrate. For example, the laminated structurecan also be formed on a well formed on the Si substrate, an SiGesubstrate, a Ge substrate, an SiGeC substrate, an SOI (silicon oninsulator) substrate formed with a thin-film semiconductor on aninsulating film, an SGOT (silicon-germanium on insulator) substrate, ora well formed on any of the substrates.

In the first to fifth embodiments, the channel region is formed in aflat structure. However, the channel region need not necessarily beflat. For example, the channel region may be formed in athree-dimensional structure, such as an FIN structure.

In the first to fifth embodiments, the elements are two-dimensionallyarranged. However, the elements need not necessarily betwo-dimensionally arranged. For example, a laminated structure or avertical structure may be adopted as the element arrangement.

The operation bias signs in the embodiments are shown by assuming ann-channel transistor on a p-type substrate, but the invention is alsoeffective for an n-type substrate. To use the n-type substrate, theoperation bias signs may be made opposite.

In the first to fifth embodiments, the source region 2 and the drainregion 3 are n-type regions. However, the source region 2 and the drainregion 3 may be p-type regions. Further, the source region 2 and thedrain region 3 may be a metal-contained conductive regions, such as ametal and a metal silicide. As the metal silicide, nickel silicide andcobalt silicide may be used, for example.

Although, in the first to fourth embodiments, the source and drainregions are formed before the gate laminated structure is formed, thesource and drain regions may be formed after the gate laminatedstructure have been formed by use of the gate laminated structure as amask.

According to an aspect of the present invention, charge emission fromthe upper insulating layer of the nonvolatile semiconductor memoryelement at the data retaining time can be effectively suppressed andthreshold fluctuation during the data retaining time in the nonvolatilesemiconductor memory element can be effectively suppressed.

According to another aspect of the present invention, there may beprovided a method for controlling a nonvolatile semiconductor memoryelement including: a semiconductor substrate including: a source regionthat is formed in the semiconductor substrate; a drain region that isformed in the semiconductor substrate; and a channel region that issandwiched between the source region and the drain region; a lowerinsulating film that is formed on the channel region; a conductivecharge storage film that is formed on the lower insulating film and thatstores data; an upper insulating film including: a first insulating filmthat is formed on the conductive charge storage film; and a secondinsulating film that is formed on the first insulating film; and acontrol gate that is formed on the upper insulating film, wherein thefirst insulating film is formed to have a trap level density larger thanthat of the second insulating film, the method including: applying avoltage having a second polarity between the control gate and thesemiconductor substrate, thereby injecting a charge having a firstpolarity opposite to the second polarity into the conductive chargestorage film from the semiconductor substrate and trapping the chargehaving the first polarity in the first insulating film; and applying avoltage having the first polarity between the control gate and thesemiconductor substrate, thereby emitting the charge having the firstpolarity trapped in the first insulating film from the first insulatingfilm to the conductive charge storage film.

According to still another aspect of the present invention, there may beprovided a method for controlling a nonvolatile semiconductor memoryelement including: a semiconductor substrate including: a source regionthat is formed in the semiconductor substrate; a drain region that isformed in the semiconductor substrate; and a channel region that issandwiched between the source region and the drain region; a lowerinsulating film that is formed on the channel region; a non-conductivecharge storage film that is formed on the lower insulating film and thatstores data; an upper insulating film including: a second insulatingfilm that is formed on the non-conductive charge storage film; and afirst insulating film that is formed on the second insulating film; anda control gate that is formed on the upper insulating film, wherein thefirst insulating film is formed to have a trap level density larger thanthat of the second insulating film, the method including: applying avoltage having a first polarity between the control gate and thesemiconductor substrate, thereby emitting a charge having the firstpolarity from the non-conductive charge storage film to thesemiconductor substrate and trapping the charge having the firstpolarity in the first insulating film; and applying a voltage having asecond polarity opposite to the first polarity between the control gateand the semiconductor substrate, thereby emitting the charge having thefirst polarity trapped in the first insulating film from the firstinsulating film to the control gate.

What is claimed is:
 1. A nonvolatile semiconductor memory elementcomprising: a semiconductor substrate; a lower insulating film that isdisposed on the semiconductor substrate; a charge storage film that isdisposed on the lower insulating film; an upper insulating film that isdisposed on the charge storage film; and a control gate that is disposedon the upper insulating film; wherein the upper insulating filmincludes: a first insulating film having a thickness of 4 nm or less; asecond insulating film that is disposed on the first insulating film;and a third insulating film that is disposed on the second insulatingfilm, wherein the third insulating film is an SiO2 film, and wherein athickness of the first insulating film is thinner than that of the thirdinsulating film.
 2. The nonvolatile semiconductor memory elementaccording to claim 1, wherein the second insulating film includes atleast one film selected from a group consisting of: an oxide film of Ti,Y, Zr, or Hf; a nitride film of Ti, Y, Zr, or Hf; and an oxynitride filmof Ti, Y, Zr, or Hf.
 3. The nonvolatile semiconductor memory elementaccording to claim 1, wherein the second insulating film includes HfSiO.4. The nonvolatile semiconductor memory element according to claim 1,wherein the first insulating film includes at least one film selectedfrom a group consisting of: an SiO2 film; an SiON film; an SiN film; anAl2O3 film; and an LaAlSiO film.
 5. The nonvolatile semiconductor memoryelement according to claim 1, wherein the charge storage film includesSi.
 6. The nonvolatile semiconductor memory element according to claim1, wherein the control gate includes at least one film selected from agroup consisting of: a nitride of W, Ti, or Ta; and a carbide of W, Ti,or Ta.
 7. The nonvolatile semiconductor memory element according toclaim 1, wherein the second insulating film includes at least one filmselected from a group consisting of: an oxide film of Ti, Y, Zr, or Hf;a nitride film of Ti, Y, Zr, or Hf; and an oxynitride film of Ti, Y, Zr,or Hf, wherein the first insulating film includes at least one filmselected from a group consisting of: an SiO2 film; an SiON film; an SiNfilm; an Al2O3 film; and a LaAlSiO film; wherein the charge storage filmincludes Si, and wherein the control gate includes at least one filmselected from a group consisting of: a nitride of W, Ti, or Ta; and acarbide of W, Ti, or Ta.
 8. The nonvolatile semiconductor memory elementaccording to claim 1, wherein a leakage of the first insulating film islarger than that of the third insulating film.
 9. A nonvolatilesemiconductor memory comprising: a memory cell array including aplurality of nonvolatile semiconductor memory elements according toclaim 1; and a detrap pulse supply circuit that applies a detrap pulseto the control gate so as to pull out a charge from the secondinsulating film after the data has been written to the charge storagefilm.